18716-80-8Relevant academic research and scientific papers
Reaction of potassium tetracarbonylhydridoferrate with aryl halides: mechanistic study and extension to the catalytic carbonylation of iodobenzene by a bimetallic Fe(CO)5-Co2(CO)8 system
Brunet,de Montauzon,Taillefer
, p. 341 - 346 (1991)
Potassium tetracarbonylhydriodoferrate, KHFe(CO)4, reacts with aryl iodides in wet methanol to yield the corresponding arenes. This reaction is catalytic under carbon monoxide (1 atm) in the presence of an excess of base. Mechanistic investigations, both by IR analysis and by electrochemical experiments, show that the reaction involves an electron transfer from HFe(CO)4- to the aryl halide to generate the corresponding radical anion. The resulting aryl radical either abstracts an hydrogen atom from potassium methoxide of combines with the [HFe(CO)4] radical species to form ArFe(H)(CO)4, which yields ArH by reductive elimination. The catalytic carbonylation of iodobenzene to benzoic acid can be performed under very mild conditions by a bimetallic system, viz. HFe(CO)4--Co(CO)4-. The observed synergetic effect is believed to involve first an electron transfer from HFe(CO)4- to iodobenzene and generation of a phenyl radical, followed by reaction with Co(CO)4-, which acts as the actual carbonylation catalyst. In agreement with these hypotheses, the carbonylation of bromobenzene, which on its own is unreaction under these conditions, can be promoted by the presence of iodobenzene.
Thiolate, Thioether, and Thiol Derivatives of Iron(0) Carbonyls
Liaw, Wen-Feng,Kim, Christine,Darensbourg, Marcetta Y.,Rheingold, Arnold L.
, p. 3591 - 3597 (2007/10/02)
A new series of anionic complexes of iron tetracarbonyl monofunctionalized with the ligand ->,-> (R = Ph, Et, Me, H), have been synthesized and characterized.The compound was formed in the reaction of and PhSSPh.The -> anion was characterized by X-ray diffraction as its +> salt and found to be a typical trigonal-bipyramidal complex in which the phenylthiolate ligand occupies an axial position with a Fe-S bond distance of 2.332(5) Angstroem and Fe-S-C(Ph) = 111.3(6) deg.The salt crystallized inthe orthorhombic space group Pbc21, with a = 9.529(4) Angstroem, b = 21.493(9) Angstroem, c = 20.185(9) Angstroem, V = 4134(3) Angstroem3, and Z = 2.Other members of the series of complexes, ->, were best obtained by ligand exchange of -> and the labile thioether complex (PhSMe)Fe(CO)4.The latter was produced from the low-temperature alkylation of the ->.Protonation of the thiolates (R = Ph, Et, Me, H) ultimately leads to formation of H2 and Fe2(μ-SR)2(CO)6; however, the intermediate thiol, (RSH)Fe(CO)4, could be observed at -78 to -40 deg C for R = Et, Me.The PhSH and HSH derivatives were unstable even at -78 deg C.
Synthesis of bimetallic Fe-Ni carbonyl clusters: Crystal structure of [N(CH3)3CH2Ph][Fe3Ni(CO) 8(μ-CO)4(μ3-H)]
Ceriotti, Alessandro,Chini, Paolo,Fumagalli, Alessandro,Koetzle, Thomas F.,Longoni, Giuliano,Takusagawa, Fusao
, p. 1363 - 1368 (2008/10/08)
Redox condensation of [Fe3(CO)11]2- with Ni(CO)4 in tetrahydrofuran affords the tetranuclear dianion [Fe3Ni(CO)12]2-. Subsequent protonation with acids results in formation of the corresponding [Fe3Ni(CO)12H]- anion. This monoanionic species has also been obtained by reaction of [Fe3(CO)11]2- with NiCl2·xEtOH. Both Fe3Ni systems have been isolated in the solid state in high yield with a variety of tetrasubstituted ammonium and phosphonium salts. An X-ray diffraction study of the trimethylbenzylammonium salt of [Fe3Ni(CO)12H]- reveals a structure with a tetrahedron of metal atoms surrounded by eight terminal and four edge-bridging carbonyl groups. The hydride ligand has been located over the center of an Fe2Ni face at a distance of 0.60 (3) A? from the trimetal plane. The corresponding [Fe3Ni(CO)12]2- dianion is suggested to posses an analogous structure on the basis of its IR spectrum. Crystallographic data for [C10H16N]+[C12HFe 3NiO12]-: fw 713.64, triclinic, space group P1, Z = 2, a = 7.416 (1) A?, b = 13.849 (2) A?, c = 14.108 (2) A?, α = 103.13 (2)°, β = 103.15 (2)°, γ = 99.23 (2)°, R(F2) = 0.030 for 3860 reflections measured at room temperature.
